JP2541292B2 - Method for producing impact-resistant polyamide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a polyamide resin composition which can be used as various molded articles, sheets or films by injection molding or extrusion molding.

More specifically, a polyamide resin composition obtained by melt-kneading a polyamide resin and an unsaturated dicarboxylic acid anhydride-modified olefin polymer by a special compounding method has excellent impact resistance, good balance of other physical properties, and good processability. Of the manufacturing method of.

[Conventional technology]

Generally, polyamide resin is widely used as an engineering plastic because of its excellent rigidity, abrasion resistance, chemical resistance, heat resistance, and electrical characteristics.

However, they have difficulties or need improvement in impact resistance, molding stability, etc., and these are obstacles in cultivating practical applications.

Various methods have been proposed to improve the impact resistance, which is a disadvantage of such polyamide resins.

For example, as typical methods, JP-A-53-146754, JP-B-54-4743, JP-B-55-44108,
As described in Japanese Patent Laid-Open No. 58-23850,
Examples thereof include a method of adding a modified ethylene copolymer type polymer having an active group capable of reacting with a polyamide resin and rubber elasticity.

However, according to the study results of the present inventors, it is possible to obtain a molded article having relatively improved impact resistance in the above-mentioned conventional technique, but it is still insufficient. It was also found that it was not satisfactory from the viewpoint of the balance of physical properties such as heat resistance, rigidity and impact resistance.

That is, its somewhat improved impact resistance and flexibility is offset by mechanical properties that are significantly poorer than the polyamide resin itself, such as stiffness, tensile strength, hardness, heat resistance, and the like. Furthermore, there are many problems such that a colored molded product having an unsatisfactory appearance is often obtained, and the application is limited.

Therefore, it is important to select a modified ethylene copolymer type polymer to be added to the polyamide resin, which does not cause the above problems, and its development is strongly desired.

[Problems to be Solved by the Invention]

In order to improve impact resistance, which is a drawback of such a polyamide resin, the present invention melt-kneads a specific unsaturated dicarboxylic acid anhydride olefin polymer by a special compounding method to obtain mechanical properties such as heat resistance and rigidity. In order to solve the above problems without compromising the above, the purpose is to use polyamide resin as the main component.
It is an object of the present invention to provide a method for producing a polyamide resin composition having excellent impact resistance, mechanical properties such as heat resistance and rigidity, and excellent flow characteristics.

[Means for solving the problem]

From this viewpoint, the present inventors have extensively and densely searched for a method for producing a resin composition effective for modifying a polyamide resin, and as a result, melt-kneaded a modified olefin polymer having a specific structure with a special compounding method. It was found that, by doing so, a composition with a good balance of impact resistance, heat resistance, and rigidity, and in which the appearance of molded products and molded products was excellent, was obtained.
The present invention has been reached.

That is, the present invention comprises 60 to 20 parts by weight of component (A) polyamide resin, and component (B) olefin rubber, α-olefin polymer, crystalline ethylene / α-olefin copolymer and ethylene / ethylenically unsaturated ester. Modified olefin polymer obtained by melt-kneading 100 parts by weight of at least one olefin polymer having a glass transition point of -10 ° C or lower and 0.1 to 10 parts by weight of unsaturated dicarboxylic acid anhydride selected from copolymers. To 80 parts by weight of the composition (I) obtained by melt-kneading in the former stage, and further in the latter stage, the component (C) has reactivity with a carboxyl group, a carboxylic acid anhydride group and an amino group. Component (D) polyamide resin 50-1000 per 100 parts by weight of composition (II) obtained by adding 0.01 to 20 parts by weight of a polyfunctional compound containing two or more functional groups in one molecule and melt-kneading Melt parts by weight The present invention relates to a method for producing an impact-resistant polyamide resin composition characterized by melt-kneading.

As the polyamide resin as the component (A) and the component (D) in the present invention, various polyamides obtained by polycondensation of a lactam having three or more membered rings, a polymerizable ω-amino acid, a dibasic acid and a diamine, etc. are used. be able to.

Specifically, polymers such as ε-caprolactam, aminocaproic acid, enantolactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, or butanediamine,
Diamines such as hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylenediamine and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid and glutaric acid Polymers obtained by polycondensation of or copolymers thereof are mentioned.

Specific examples include polyamide 4.6, polyamide 6, polyamide 6.6, polyamide 6.10, polyamide 11, polyamide 12,
Aliphatic polyamide resins such as polyamide 6.12, polyhexamethylenediamine terephthalamide, polyhexamethylene isophthalamide, aromatic polyamide resins such as polyamides containing xylene groups.

Of these, polyamide 6, polyamide 6.6, and polyamide 12 are particularly preferable.

In addition, various copolymer nylon resins with a melting point of 80 to 200 ° C, which are commercially available for hot melt adhesives, are also available.
It can be applied alone or in combination with a polyamide having a melting point of 200 ° C or higher.

In the present invention, the polyamide resins that are the components (A) and (D) may be the same polyamide resin or different polyamide resins.

The unsaturated dicarboxylic acid anhydride-modified olefin polymer used in the component (B) of the present invention is an olefin rubber, an α-olefin polymer, a crystalline ethylene / α-olefin copolymer, an ethylene / ethylenically unsaturated ester. Modification by melting and kneading a composition consisting of 100 parts by weight of at least one olefin polymer having a glass transition temperature of -10 ° C or lower selected from copolymers and 0.1 to 10 parts by weight of unsaturated carboxylic acid anhydride It is an olefin polymer.

As olefin rubber, ethylene and carbon number 3
A rubber composed of a copolymer of at least one α-olefin may be mentioned. For example, ethylene and propylene, butene-1,
Examples thereof include copolymer rubbers with hexene-1,4-methylbutene-1 or 4-methylpentene-1. Particularly suitable is a copolymer rubber of ethylene and propylene. Further, these ethylene copolymer rubbers further contain non-conjugated dienes such as methylene norbornene, ethylidene norbornene, 1,4-hexadiene and dicyclopentadiene, in addition to ethylene and α-olefins having 3 or more carbon atoms. It may be a three-element polymer. In addition, butyl rubber,
Other examples include ethylene / acrylic ester copolymer rubber.

Examples of the α-olefin polymer and the crystalline ethylene / α-olefin copolymer include polyisobutylene, a crystalline propylene / ethylene copolymer, and a crystalline ethylene / butylene copolymer.

As the ethylene / ethylenically unsaturated ester copolymer, ethylene / α, β-unsaturated carboxylic acid alkyl ester and / or carboxylic acid vinyl ester copolymer can be used. For example, ethylene and methyl acrylate,
Examples include copolymers with one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, and vinyl acetate. Ethylene / methyl methacrylate copolymer,
Ethylene / vinyl acetate copolymer is preferred.

The olefin polymer used in the present invention is an olefin polymer having a glass transition point of -10 ° C or lower. When the glass transition point of the olefin polymer exceeds -10 ° C, the impact resistance improving effect on the polyamide resin becomes insufficient.

Examples of unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, hymic acid anhydride, tetrahydrophthalic anhydride, and bicyclo (2,2,
2) Oct-5-ene-2,3-dicarboxylic acid anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic acid anhydride, 1,2,3,4,5,8,9, 10-octahydronaphthalene-2,3-
Dicarboxylic acid anhydride, 7-oxabicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic acid anhydride and the like can be mentioned. Of these, maleic anhydride is particularly preferably used.

The unsaturated carboxylic acid anhydride-modified olefin polymer in the present invention is produced by melt-kneading 100 parts by weight of the olefin polymer and 0.1 to 10 parts by weight of the unsaturated dicarboxylic acid anhydride. If the amount of the unsaturated dicarboxylic acid anhydride used is less than 0.1 parts by weight, the impact resistance improving effect on the polyamide resin will be insufficient. If the amount of the unsaturated dicarboxylic acid anhydride used exceeds 10 parts by weight, the amount of the gelled product is increased, which is not preferable.

When melt-kneading the unsaturated dicarboxylic acid anhydride, it is preferable to add a radical polymerization initiator which effectively generates radicals at the melt-kneading temperature. Radical polymerization initiators include 1,3-bis (t-butylperoxypropyl) benzene, 1,1-bis (t-butylperoxy) 3,
Organic peroxides such as 3,5-trimethylcyclohexane, t-butylperoxylaurate, dicumyl peroxide and benzoyl peroxide are preferably used.
The amount of the radical polymerization initiator used is preferably 0.01 to 5 parts by weight, more preferably 0.002 to 2 parts by weight, based on 100 parts by weight of the olefin polymer.

When melt-kneading the unsaturated dicarboxylic acid anhydride, the aromatic vinyl monomer such as styrene is added in an amount of 0.1 to 5 parts by weight per 1 part by weight of the unsaturated dicarboxylic acid anhydride (based on 100 parts by weight of the olefin polymer). Equivalent to 0.01 to 50 parts by weight),
Preferably 0.2 to 3 parts by weight (equal to 0.02 to 30 parts by weight)
This is a very preferable method for carrying out the present invention, since the addition of the gelled substance can be suppressed and the amount of the unsaturated dicarboxylic acid anhydride added to the olefin polymer can be improved by adding it.

The temperature for melt-kneading the olefin polymer and the unsaturated dicarboxylic acid anhydride is preferably 180 to 300 ° C. The kneading machine is not particularly limited, but it is generally preferable to use an extruder from the viewpoint of continuous production.

Component (C) used in the present invention is a modified olefin polymer, which is a polyfunctional compound containing two or more functional groups reactive with a carboxyl group, a carboxylic acid anhydride group and an amino group in one molecule. (B) or polyamide resin (A)
On the other hand, the compound is not particularly limited as long as it has intermolecular crosslinking reactivity, but specific examples are given below.

As the polyfunctional compound which is the component (C), for example, two or more functional groups selected from amino group, epoxy group, dihydrooxazolyl group, carboxyl group, carboxylic acid anhydride group and hydroxyl group are contained in one molecule. The compound which does can be mentioned. The molecular weight of the polyfunctional compound (C) is not particularly limited, and includes high molecular compounds.

Specific examples of compounds containing two or more amino groups in one molecule are shown below.

For example, aliphatic diamines such as 1,6-hexamethylenediamine, trimethylhexamethylenediamine, 1,4 diaminobutane, 1,3 diaminopropane, ethylenediamine and polyetherdiamine, and aliphatic diamines such as hexamethylenediamine carbamate and ethylenediamine carbamate. Diamine carbamates, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, ethylaminoethylamine, methylaminopropylamine, 2-hydroxyethylaminopropylamine, aminoethylethanolamine, 1,3-bis (3-amino Propoxy) -2,2-dimethylpropane, 1,
Aliphatic polyamines such as 3,6-trisaminomethylhexane, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine, menthenediamine, N-aminoethylpiperazine, 1,3-diaminocyclohexane, Isophorone diamine, bis (4-
Alicyclic polyamines such as amino-3-methylcyclohexyl) methane, aliphatic polyamines having aromatic groups such as m-xylylenediamine, diaminodiphenyl ether, 4,
4'-methylenedianiline, diaminodiphenyl sulfone, benzidine, 4,4'-bis (o-toluidine), 4,4 '
-Thiodianiline, dianisidine, methylenebis (o-
Aromatic amines such as chloroaniline), bis (3,4-diaminophenyl) sulfone and diaminoditolylsulfone, 1,3-bis (γ-aminopropyl) -1,1,3,3-tetramethyldicyclo Silicon-containing polyamines such as xane, amine-modified silicone oil, and butadiene-acrylonitrile copolymer whose terminal functional group is amine,
N, N, N ', N'-tetramethylhexamethylenediamine, N,
Tertiary amine compounds such as N, N ', N ", N" -pentamethyldiethylenetriamine and ethylene units such as ethylene and N, N-dimethylaminoethylmethacrylate copolymers
Ethylene copolymers consisting of N, N-dialkylaminoalkyl α, β-unsaturated carboxylic acid ester units, ethylene units such as copolymers of ethylene and N, N-dimethylaminopropylacrylamide, and N, N-dialkylaminoalkyl An ethylene copolymer or the like composed of α, β-unsaturated carboxylic acid amide units can also be used.

Specific examples of compounds containing two or more epoxy groups in one molecule are given below.

It is roughly classified into an epoxy group-containing olefin-based copolymer and an epoxy compound.

As the epoxy group-containing olefin-based copolymer, a copolymer of olefins and glycidyl methacrylate and / or glycidyl acrylate can be used. As olefins, ethylene, propylene, butene-
1, isobutylene and the like can be mentioned, of which ethylene is particularly preferable. Furthermore, as a copolymer component,
It may contain α, β-unsaturated carboxylic acid alkyl ester and carboxylic acid vinyl ester. For example, an alkyl ester of acrylic acid, methacrylic acid, etc., and specific examples include methyl acrylate, ethyl acrylate,
Examples thereof include n-butyl acrylate, methyl methacrylate, vinyl acetate, vinyl propionate and the like. Further, glycidyl methacrylate modified ethylene-propylene rubber, ethylene-methyl acrylate-glycidyl methacrylate copolymer rubber and the like can be mentioned.

The polymerization method may be one produced by any of random copolymerization, block copolymerization, and graft copolymerization. The content of glycidyl methacrylate and / or glycidyl acrylate units in the olefin-based copolymer is selected to be 1 to 50% by weight, and outside this range, the effect of improving the physical properties of the present invention is insufficient.

Examples of the epoxy compound include bisphenols such as bisphenol A, resorcinol, and hydroquinone, and glycidyl ethers of these halogenated bisphenols. Among them, epoxy resins are preferable.

These epoxy compounds are used alone or as a mixture of two or more kinds.

Generally, an epoxy compound is used by blending a curing agent such as amines, acid anhydrides, polymercaptans, and phenol resins. In the present invention, it is usual to use no curing agent, but the amount of active hydrogen Can be used as long as it has an equimolar ratio to the epoxy group component or less.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type resin, glycidyl amine type resin, hydantoin type epoxy resin and triglycidyl isocyanurate. Can be mentioned.

Examples of the compound containing two or more hydroxyl groups in one molecule include trimethylolpropane, pentaerythritol, and a saponified product of a copolymer of ethylene and vinyl acetate.

A compound containing two or more dihydrooxazolyl groups in one molecule can also be used, and is a copolymer of 2,2 '-(1,3-phenylene) -bis (2-oxazoline), styrene and vinyloxazoline. Etc.

In the polyamide resin composition according to the present invention, the content of the polyamide resin as the component (A) in the composition (I) is 60 to 60%.
20 parts by weight, the modified olefin polymer of component (B) is 40
-80 parts by weight are included. When the content of the polyamide resin component (A) in the composition (I) is less than 20 parts by weight, the rigidity and heat resistance are insufficient, and when it exceeds 60 parts by weight, favorable results cannot be obtained in impact resistance.

In the present invention, the addition amount of the polyfunctional compound of the component (C) needs to be adjusted by the reactivity of the functional group of the polyfunctional compound with respect to a carboxyl group, a carboxylic acid anhydride group and an amino group. Total amount of component (A) and modified olefin polymer component (B) (composition (I)) 100
It is 0.01 to 20 parts by weight with respect to parts by weight. In this way, the composition (II) can be obtained. In the composition (II), when the amount of the polyfunctional compound as the component (C) added is less than 0.01 parts by weight, the effect of improving mechanical properties such as heat resistance and rigidity is small, and
If it exceeds 20 parts by weight, the effect of increasing the amount cannot be recognized.

The addition amount of the polyamide resin of the component (D) in the present invention is 50 to 1000 parts by weight with respect to 100 parts by weight of the composition (II). If it is less than 50 parts by weight, the rigidity and heat resistance are insufficient,
If it exceeds 0 parts by weight, favorable results cannot be obtained in impact resistance.

The method for producing the polyamide resin composition of the present invention is a method of kneading in a molten state. The compounding method is such that a polyfunctional compound (C) is added to a partially crosslinked composition (I) obtained by melt-kneading a polyamide resin component (A) and a modified olefin polymer component (B). This is a method in which the component (II) obtained by the partial cross-linking reaction is obtained by melt-kneading, and the component (D) polyamide resin is further added in the latter stage and melt-kneading is performed.

The polyamide resin composition according to the present invention has a very good balance of mechanical properties such as impact resistance and physical properties of molded articles such as thermal properties. In particular, by adding the component (D) polyamide resin in the latter stage and melt-kneading, the rigidity is increased and the melt index is increased to improve the processing method.

In the present invention, the reason why a remarkable effect of improving the physical properties occurs by melt-kneading by the special compounding method specified as described above is that a micro-dispersed state of a polymer having good physical properties occurs due to an appropriate crosslinking action. It is believed that there is.

Polyamide resin (A) and modified olefin polymer (B)
When melt-kneading, the melting point of the modified olefin polymer is lower than the melting point of the polyamide resin, so that the modified olefin polymer becomes the matrix phase at the initial stage of melt-kneading. When the melt-kneading is further continued and the polyamide resin as the component (D) is added, the volume of the polyamide resin component becomes larger than the volume of the modified olefin polymer, so that the polyamide resin undergoes phase inversion to the matrix phase. Therefore, in the present invention, the phase inversion is stopped at an intermediate stage by adding a partial crosslinking agent composed of a polyfunctional compound.

As a result, the modified olefin polymer phase containing the polyamide resin particles is dispersed in the polyamide resin in a multi-dispersed state, which is similar to impact-resistant polystyrene and produces the best physical properties. It is considered to be in a dispersed state.

The shape and size of the modified olefin polymer phase are not essentially specified. In that sense, if the particle diameter of the rubbery dispersed phase such as the olefin polymer component is, for example, 1 micron or less, the improvement effect is excellent to some extent (Japanese Patent Publication No. 55-44108, Japanese Patent Laid-Open No. 61-108108). -1
It can be said that it is a new technical idea that is clearly distinguished from (described in 63960 gazette, etc.).

Generally, if the thermal deformation resistance is improved, the rigidity tends to increase and the impact resistance tends to decrease. On the other hand, in the composition according to the present invention, the heat resistance without decreasing other physical properties,
Improving the impact resistance in a well-balanced manner is unpredictable and expensive.

For the melt kneading, generally used kneading devices such as a single-screw or twin-screw extruder, a Banbury mixer, a roll, and various kneaders can be used.

To add and melt-knead the polyfunctional compound component (C) of the present invention, the polyamide resin component (A) can be prepared, for example, by an extruder.
Alternatively, the melt-kneaded composition of the modified olefin polymer component (B) and the modified olefin polymer component (B) may be once granulated and produced, then the polyfunctional compound component (C) may be added, and the mixture may be melt-kneaded again with an extruder. Preferably, an extruder equipped with a side feed device is used to produce a melt-kneaded composition of the polyamide resin component (A) and the modified olefin polymer component (B) in the former stage (front part), and the latter stage of the same extruder ( In the rear part), it is preferable that the polyfunctional compound component (C) in the solid or molten state is added by a side feed device and the mixture is melt-kneaded.

Further, a multifunctional compound component (C) and a resin which is inactive with respect to the multifunctional compound component (C) are melt-kneaded in advance to prepare a masterbatch to produce the thermoplastic resin composition of the present invention. It is also a preferable method to add an appropriate amount and melt-knead.

To add and melt-knead the polyamide resin of the component (D) of the present invention, for example, a composition (I) obtained by melt-kneading the polyamide resin component (A) and the modified olefin polymer component (B) with an extruder. After the composition (II) consisting of the polyfunctional compound (C) and the polyfunctional compound (C) is once granulated and produced, the component (D) is added.
The polyamide resin can be added and melt-kneaded again with an extruder, but it can be preferably produced using an extruder with a side feed device. That is, first, the polyamide resin component (A) and the modified olefin polymer component (B) are melt-kneaded in the first stage (front part) to obtain the composition (I), and then in the middle stage (middle part) by a side feed device. A functional compound (C) is added to produce a composition (II), and a component (D) in a molten state or a solid state is similarly produced by a side feed device in the latter stage (rear part) of the same extruder.
It is preferable that the polyamide resin is added and melt-kneaded.

Further, in the present invention, the object of the present invention can be achieved even by simple melt-kneading such as in an injection molding machine. That is, for example, the granulated pellet of the composition (II) and the component (D)
Polyamide resin is mixed by dry blending method,
By direct injection molding, molded products with good physical properties can be obtained all at once.

In the method according to the present invention, at the time of kneading, it is preferable that all the resin components are in the form of powder or pellets and are uniformly mixed in advance with a device such as a tumbler or a Henschel mixer. It is also possible to use a method of omitting the mixing and supplying the kneading device separately in a fixed amount.

The resin composition obtained by the present invention has a moldability,
As long as the physical properties are not impaired, other components such as pigments,
Additives such as dyes, reinforcing agents, fillers, heat stabilizers, antioxidants, weatherproofing agents, nucleating agents, lubricants, antistatic agents, flame retardants, plasticizers, or other polymers, etc. You can

In particular, when a reinforcing agent or a filler such as glass fiber, carbon fiber, talc, calcium carbonate or magnesium hydroxide which has been subjected to various surface treatments is added to the resin composition of the present invention,
An extremely useful material having high rigidity and high impact strength can be obtained.

The resin composition obtained by the present invention is molded by injection molding, extrusion molding and various other molding processability.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

The flexural modulus (sample thickness 3.2 mm, measuring temperature 23 ° C) in the examples is JIS K7203, and the Izod impact strength (sample thickness 3.2 mm, measuring temperature 23 ° C and -40 ° C, with V-notch) is JIS K7203. Performed according to K7110. NB is 50 kg · cm / cm or more, indicating that the test piece did not break.

Heat distortion temperature (sample thickness 3.2mm, bending stress 4.6Kgf / c
m ² ) is JIS K7207, melt index (MI, 2160g)
Was carried out according to JIS K6760, respectively.

The amount of added maleic anhydride in the modified olefin polymer is
A small amount of the extruded sample was dissolved in xylene and purified by precipitation with anhydrous acetone. Then, it was made into a xylene solution again and heated with phenolphthalein as an indicator (85
(° C) was titrated with a KOH ethanol solution.

In the present examples and comparative examples, the following were used as the polyamide resin, modified olefin polymer and polyfunctional compound.

(A) and (D) Polyamide resin (1) Polyamide 66 Maranyl A 125 (Unitika Ltd.
(2) Polyamide 6 A1030BRL (manufactured by Unitika Ltd.) (B) Modified olefin polymer (1) Modified polymer (1) Ethylene / propylene copolymer rubber (glass transition point-
58 ℃, propylene unit content 22% by weight, MI (230 ℃) 1.9g
/ 10 minutes) 2 parts by weight of maleic anhydride to 100 parts by weight
Substance, 1,3-bis (t-butylperoxyisopropyl)
Mixed with 0.08 parts by weight of benzene and 2 parts by weight of styrene,
Charged into a 4mφ twin-screw extruder under a nitrogen atmosphere and the resin temperature was 250
Melted and kneaded at 0 ° C. to obtain a modified polymer (1). Obtained strange
The amount of maleic anhydride added to the water-soluble polymer (1) is 1.6% by weight,
MI (230 ° C) was 0.3 g / 10 minutes.

(2) Modified polymer (2) Propylene / ethylene block copolymer (glass transition
Point -43 ° C, ethylene unit content 12.5% by weight, MI (230 ° C)
3g / 10 minutes) 1 part by weight of maleic anhydride to 100 parts by weight
Part, 1,3-bis (t-butylperoxyisopropyl)
1 part by weight of benzene, 0.5 part by weight of styrene, antioxidant I
rganox 0.110 parts by weight of 1010 is mixed and used in a 44 mφ twin-screw extruder.
Put in nitrogen atmosphere, melt knead at resin temperature 230 ℃
Thus, a modified polymer (2) was obtained. Obtained modified polymerization
The amount of maleic anhydride added to body (2) was 0.3% by weight, MI (230
C) was 4.5 g / 10 minutes.

(3) Modified polymer (3) Ethylene / methyl methacrylate copolymer (glass transition point -34 ° C, methyl methacrylate unit content 38% by weight, MI
(190 ° C, 7g / 10min) 100 parts by weight, 1 part by weight of maleic anhydride and 0.1 part by weight of t-butylperoxylaurate were mixed and charged into a 30 mmφ twin-screw extruder under a nitrogen atmosphere. The modified polymer (3) was obtained by melt-kneading at a resin temperature of 200 ° C. The modified polymer (3) thus obtained had a maleic anhydride addition amount of 0.3% by weight and an MI (190 ° C.) of 4 g / 10 minutes.

(C) Polyfunctional compound (1) MB-1 30mmφ Using a single screw extruder with a vent, at 150 ℃, 5 parts by weight of hexamethylenediamine carbamate and Glyron CF6S
A masterbatch prepared by melt-kneading 95 parts by weight of (Copolyamide resin manufactured by MUS).

(2) Bond First E (Sumitomo Chemical Co., Ltd.) Ethylene / glycidyl methacrylate copolymer Glycidyl methacrylate unit content 12% by weight, MI (190
℃) 3g / 10 minutes (3) E-DAM copolymer ethylene / dimethylaminoethyl methacrylate copolymer
Body dimethylaminoethyl methacrylate unit content 28 times
%, MI (190 ℃) 100g / 10min (4) E-VA saponified ethylene / vinyl acetate copolymer (vinyl acetate unit content
43% by weight, MI (190 ℃) 70g / 10min) saponified product (saponification rate)
99%, MI (190 ° C) 35g / 10min) (5) MB-2 30mmφ Using a single screw extruder with a vent, at 200 ° C 2,2'-
Add (1,3-phenylene) -bis (2-oxazoline) to 5
Weight part and lift Melt and mix 95 parts by weight of WH303
Prepared masterbatch.

 A lift WH303: Ethylene / methyl methacrylate
Polymer (Sumitomo Chemical Co., Ltd.) Methyl methacrylate unit content
18% by weight, MI (190 ° C) 7 g / 10 minutes Examples 1 to 9 Using a single screw extruder with a 30 mmφ vent device,
Degree (270 ° C for polyamide 66, 6 for polyamide 6
Is 240 ° C), and the components (A) shown in Tables 1 and 2
And the component (B) were melt-kneaded to obtain a composition (I).

The composition (I) is mixed with the component (C) shown in Table 1, and the same 30 mmφ vented single-screw extruder is used at a predetermined temperature (270 ° C. for polyamide 66, 240 ° C. for polyamide 6). And melt-kneaded to obtain a composition (II).

Furthermore, using a twin-screw extruder equipped with a 44 mmφ side feed and vent device, the component (D) shown in Table 1 was melted at a specified temperature (270 ° C for polyamide 66, 240 ° C for polyamide 6). While kneading, the composition (II) was quantitatively added from a side feed device installed in the middle of the extruder barrel and melt-kneaded to obtain a polyamide resin composition.

The melt index of the obtained resin composition was as shown in Table 1.

Each resin composition was dried at 80 ° C for 12 hours and then used as a molding machine with a 10 ounce injection molding machine (Toshiba IS-150-
V type) at a specified temperature (in the case of polyamide 66, 290
C., 260 ° C. for polyamide 6, and a mold temperature of 70 ° C., and a test piece for measuring physical properties was prepared.

The flexural modulus, Izod impact strength and heat distortion temperature of the obtained test piece were as shown in Table 1.

Comparative Examples 1 and 6 Using a single-screw extruder equipped with a 30 mmφ venting device, at a predetermined temperature (270 ° C. for polyamide 66, 240 ° C. for polyamide 6), the components (A) and components shown in Table 2 were used. (B) was melt-kneaded to obtain a composition.

The composition (C) shown in Table 2 is mixed with this composition and melted at a predetermined temperature (270 ° C. for polyamide 66, 240 ° C. for polyamide 6) using a twin screw extruder with a 44 mmφ vent. The resin composition was obtained by kneading.

The results of evaluating each resin composition in the same manner as in Example 1 are as shown in Table 2.

Compared to Examples 1 and 8, flow characteristics, rigidity,
The heat denaturation temperature is inferior.

Comparative Example 2 Using a 44 mmφ vented twin-screw extruder, at 240 ° C.
The components (A), (B) and (C) shown in the table were collectively mixed and melt-kneaded to obtain a resin composition.

The results of evaluating the resin composition in the same manner as in Example 1 are as shown in Table 2. Compared with Example 1, the Izod impact strength is inferior.

Comparative Example 3 Using a single screw extruder with a 30 mmφ venting device at 240 ° C.
Component (A) and component (B) shown in Table 2 were melt-kneaded to obtain a resin composition.

The results of evaluating each resin composition in the same manner as in Example 1 are as shown in Table 2.

Compared to Example 1, the flow characteristics, rigidity, and heat denaturation temperature are inferior.

Comparative Example 4 Components (A) and (C) shown in Table 2 were melt-kneaded at 240 ° C. using a single-screw extruder equipped with a 30 mmφ vent device.
A composition was obtained.

Further, using a twin-screw extruder equipped with a 44 mmφ side feed and vent device, while melt-kneading the second component shown in Table 2 at 240 ° C, the above composition was obtained from the side feed device installed in the middle of the extruder barrel. Was quantitatively added and melt-kneaded to obtain a resin composition.

The results of evaluating the resin composition in the same manner as in Examples are as shown in Table 2. Compared with Example 2, the Izod impact strength is inferior.

Comparative Examples 5 and 7 Polyamide 6 or polyamide 66 was molded in the same manner as in Example 1 and the physical properties were measured. The results are shown in Table 2.

[Effects of the Invention] As described above, according to the present invention, the balance of mechanical properties such as impact resistance and the physical properties of molded articles such as thermal properties is very good, and the appearance is also remarkable. It is possible to provide a method for producing a polyamide resin composition that exhibits various effects.

In particular, it can be said that the unpredictable improvement effect was that the heat distortion resistance could be improved without lowering the impact resistance by melt-kneading with a special two-stage method.

Furthermore, the impact-resistant polyamide resin composition provided by the present invention has good flow properties and can be easily molded by molding methods such as injection molding and extrusion molding used for ordinary polyamide resin compositions. Product, film,
It is processed into a sheet, etc., and has a good balance of physical properties such as impact resistance, rigidity, heat resistance, etc., and provides a product with excellent appearance uniformity and smoothness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noboru Yamaguchi 5-1 Anezaki Kaigan, Ichihara City, Chiba Prefecture, Sumitomo Chemical Co., Ltd. (72) Inventor, Hitoshi Nanbu 5-1 Anezaki Kaigan, Ichihara City, Chiba Sumitomo Chemical Co., Ltd. Within

Claims (8)

(57) [Claims] 1. A component (A), a polyamide resin of 60 to 20 parts by weight, a component (B), an olefin rubber, an α-olefin polymer,
Selected from crystalline ethylene / α-olefin copolymers and ethylene / ethylenically unsaturated ester copolymers,
100 parts by weight of at least one olefin polymer having a glass transition temperature of -10 ° C or lower and 40 to 80 parts by weight of a modified olefin polymer obtained by melt-kneading 0.1 to 10 parts by weight of an unsaturated dicarboxylic acid anhydride, In addition to the component (I) obtained by melt-kneading at 2), the functional group having reactivity with the component (C) carboxyl group, carboxylic acid anhydride group, and amino group is added in 2 molecules per molecule. It is possible to melt-knead 50 to 1000 parts by weight of the component (D) polyamide resin with 100 parts by weight of the composition (II) obtained by adding 0.01 to 20 parts by weight of a polyfunctional compound containing one or more of them and melt-kneading them. A method for producing an impact-resistant polyamide resin composition, which is characterized. 2. The component (B) modified olefin polymer is selected from olefin rubbers, α-olefin polymers, crystalline ethylene / α-olefin copolymers and ethylene / ethylenically unsaturated ester copolymers. , At least one olefin polymer having a glass transition temperature of -10 ° C or lower 10
The modified olefin polymer obtained by melt-kneading 0 parts by weight, 0.1 to 10 parts by weight of an unsaturated dicarboxylic acid anhydride, and 0.01 to 50 parts by weight of an aromatic vinyl monomer. Method for producing impact-resistant polyamide resin composition. 3. The method for producing an impact-resistant polyamide resin composition according to claim 1, wherein the unsaturated dicarboxylic acid anhydride as the component (B) is maleic anhydride. 4. The method for producing an impact-resistant polyamide resin composition according to claim 3, wherein the olefin rubber as the component (B) is an ethylene / propylene copolymer rubber. 5. The component (C) polyfunctional compound is an amino group,
2. A polyfunctional compound containing two or more functional groups selected from epoxy groups and hydroxyl groups in one molecule.
A method for producing the impact-resistant polyamide resin composition described. 6. The method for producing an impact resistant polyamide resin composition according to claim 5, wherein the polyfunctional compound as the component (C) is an aliphatic diamine carbamate. 7. An ethylene copolymer or ethylene unit and an N, N-dialkyl in which the polyfunctional compound (C) is an ethylene unit and an N, N-dialkylaminoalkyl α, β-unsaturated carboxylic acid ester unit. The method for producing an impact-resistant polyamide resin composition according to claim 5, which is an ethylene copolymer comprising aminoalkyl α, β-unsaturated carboxylic acid amide units. 8. An ethylene copolymer, wherein the polyfunctional compound of component (C) comprises an ethylene unit and an α, β-unsaturated carboxylic acid glycidyl unit, an ethylene unit, an α, β-unsaturated carboxylic acid glycidyl unit and an α. 6. An ethylene copolymer comprising an .beta.-unsaturated carboxylic acid alkyl ester unit or an ethylene copolymer comprising an ethylene unit, an .alpha.,. Beta.-unsaturated carboxylic acid glycidyl unit and a carboxylic acid vinyl ester unit. Method for producing impact polyamide resin composition.